Mono-azo-dyestuffs insoluble in water



United States Patent 2,742,459 MONO-AZOPDYESTUFFS INSOLUBLEilN WATER v Ernst. Fischer, Offenbach (Main),.,Germany, assignor. to Farbwerke Hoechst Aktiengesellsjchaft. vormals Meister Lucius und Bruning, Frankfurt. (Main)-Hochst, Ger many, a company of Germany No Drawing. Application August 5, 1952,, Serial No. 302,817

ticul" ly it relates to dyestuffs corresponding to the following general formula:

wherein one of the two substituents X1 and X2 represents a halogen atom and the other represents an OR radical, R stands for a methyl or ethyl group, Y represents hydrogen, an alkoxy group or a halogen atom.

I have found. that water-insoluble mono-azo-dyestufis can be obtained by coupling in substance, on the fiber or on a substratum, adapted, for the production of lakes, the diazo compounds of 1--amino-2-alkoxy-benzene-5-carboxylic acid amides witharylamides of 2,3-hydroxy-naphthoic acid of the general formula:

wherein one of the two substituents X1 and X2 represents a halogen atom and the other represents an -OR radical,

2,742,459 Patented Apr. 17, 1956 .3- y roxrenaphth ac d y amid s o sim lar om position as applied'in the present process have already been used, according to the German patent specification 613,234, for the dyeingof' organic plastic, masses. of high molecular weight, especially of rubber and rubber-like substances. But nothing couldbe learned from this in respect of the usefulness of such combinations in other fields of application, such as textile dyeing or printing, Owing to the comparatively easy saponifiability er the rb xylic acid amid group being- Present inthe iazo components it was, on the contrary, to be, expected-that the y uffs w re not capable of resisting@ hotaqu ou alkaline treatment which is of great importancetf or the dyeing and printing of textiles. Most of the known a'zo-' dyestuffs on the fiber-are, indeed, not sufiiciently fast to boiling, whereas the dyestutfs'prepared according to the present invention show surprisingly good Propertieskof fastness. i

Bluish red to claret tints of great brilliancy areobtained which are of high industrial value: because, alsowhen applied to thefiher; aspinktints, they possess a veryv good fastness to light and at the same time an: excellent fastness towashing. I

The following examples, serve. to illustrate the invention, but they are not intended to limit it thereto:

EXAMPLE 1 lmpregndtion bath, I

9 grams of 1-.(2,3 -hydroxy-nap lthoybamino)-2,4-di methoxy-S-chlorobenzene are dissolved with 27 cc. of denatured alcohol, 3 cc. of caustic soda solution of 38 B.,

3.cc.. of formaldehyde solution ot-33 per cent strengthand 9* cc. of warm water.

R stands for a methyl or ethyl group, Y represents hydrogen, an alkoxy group or a halogen atom, and by choosing azo components free from groups imparting solubility in water, such as sulfonic acid or carboxylic acid groups.

The dyestuffs can be produced on the vegetable fiber including regenerated cellulose by dyeing or printing processes according to the known methods for the production of ice colors or they can be produced in substance. The pigment dyestuffs obtained in the latter case can be applied on textiles by padding or printing in the presence of binding agents, and, when incorporated into the spinning solutions, they can also be used for the production of spun-dyed acetate rayon and viscose rayon. Moreover, they are suitable for the preparation of very fast color lakes and, for the preparation of colored films, they can be incorporated into masses of cellulose esters or cellulose ethers, and finally, they are adapted for the dyeing of natural and artificial resins, such assthe condensation products of formaldehyde and urea, phenols or amines.

Mono-azo-dyestufis prepared from diazo compounds of 1-amino-2-alkoxybenzene-S-carboxylic acid amides and The whole is made' up to 2, liters with water of. 35C., t

l0 gramsof Turkey. redoil of. 50; per centestrength, and 20 cc. of caustic soda solution of 3.8 B. I

Developingbath 3.3 grams of 1-amino-2 nrethoxybenaenefi-carboxylic acid amide are diazotized, while cooling, in

30 cc. of water with k H 9.6, cc, of hydrochloric. acid of 15 B. and

1.6 grams of sodium nitrite dissolved in water. By adding cold water and v 20 grams of sodium acetate the whole 'is made up to 2 liters. I

A vivid bluish red, coloration at good, fastnessto boiling and h is. obtained. The dystuif corresponds to the following formlua: 1

EXAMPLE 2 Impregnation bath 6 grams of 1-(2',3-hydroxy-naphthoyl-amino)-2,5-dimethoxy-4-chlorobenzene are dissolved with 12 cc. of denatured alcohol, 3 cc. of caustic soda solution of 38 B., 9 cc. of formaldehyde solution of 33 per cent strength,

and 6 cc. of hot water. The whole is made up to 20 liters with condensed water, 100 grams of Turkey red oil of 50 per cent strength, and 50 cc. of caustic soda solution of 38 136.,

Developing bath 8.3 grams of 1-amino-Z-methoxybenzene-S-carboxylic acid amide are diazotised, while cooling, in 80 cc. of water with 24 cc. of hydrochloric acid of 15 B. and v 4 grams of sodium nitrite dissolved in water. The whole 1 is made up to 20 liters with cold water and 45 grams of sodium acetate.

A vivid pink coloration of good fastness to boiling and light is obtained. The dyestuif corresponds to the following formula: t

N CH:

OH Cl C O-NH- (SCH;

EXAMPLE 3 16 parts by weight of a dyestutl preparation of equimolar quantities of 1-(2,3-hydroxy-naphtholyl-amino)-2,5- dimethoxy-4-chlorobenzene and of the diazoamino compound of l-amino-Z-methoxybenzene-5-carboxylic acid amide with methyltaurine are dissolved with 1 i 50 parts by weight of denatured alcohol, parts by weight of caustic soda solution of 38 B. and 150 parts by weight of water of 50 C. The solution is "poured, while stirring, into" 500 parts by weight of starch tragacanththickening, to which there are added 1 l0.parts by weight of caustic soda'solution of 38 B. and

264 parts by weight ofwater.

This printing color is printed on a cotton or viscose fabric, which is then dried, steamed for 5 minutes at 102 C. in damp steam mixed with acetic acid and formic acid vapor, rinsed, soaped at the boil, rinsed once more and dried.

A bright pink is obtained of such a brilliancy and good fastness to light as hitherto could; not be obtained with azo-dyestuifs.

If 1-(2,3'-hydroxy-naphthoylamino)-2,4 dimethoxy-5- chlorobenzene is used in the dyestufi preparation instead of 1 (2,3 hydroxy naphthoylamino) 2,5 di methoxy-4-chlorobenzene, a somewhat more bluish but also brilliant pink is produced with similar good fastness properties. 7

EXAMPLE 4 8.3 parts by weight of 1-amino-2-niethoxybenzene-5- carboxylic acid amide are diazotized in the usual manner.

In order to remove the excess mineral acid, sodium acetate is added to the diazo solution, which is then stirred into an aqueous suspension of 17.9 parts by weight of 1- (2',3 hydroxy naphthoyl amino) 2,5 dimethoxy 4-chlorobenzene obtained by dissolving this compound in dilute caustic soda solution and precipitating with acetic acid. The dyestuff which is rapidly formed on heating to 40 C. is filtered off after completion of the coupling, washed well, and dried. It constitutes a red powder which can be used for the production of a pigment print on textiles by one of the usual methods, for instance, by using an emulsion of polyvinyl acetate and the watersoluble, hardenable condensate of urea and formaldehyde. The print so obtained shows a vivid red tint and possesses good fastness properties, especially a very good fastness to light.

' EXAMPLE 5 8.3 parts by weight of 1-amino-2-methoxybenzene-5- carboxylic acid amide are diazotized in the usual manner. The diazo solution rendered neutral to Congo-papet' with sodium acetate is stirred into a suspension of 17.9 parts by weight of l-(2',3-hydroxy-naphthoyl-arnino)-2,4-dimethoxy-S-chlorobenzene prepared by dissolving it in alcohol and dilute caustic soda solution and precipitating it with acetic acid. On heating to 40 C. a red dyestuft' is rapidly formed, which, after completion of the coupling, is filtered 01f, washed well, and dried. The lacquers prepared by means of this dyestuif yield vivid red tints of good fastness to oil and light having also an excellent fastness to overspraying.

The dyestufi corresponds to the following formula:

C O-NHI HIC O O CH;

The coupling can also be carried out in the presence of a vehicle suitable for the prepartion of color lakes.

EXAMPLE 6 If in Example 5 20.1 parts by weight of l-(2,3'-hydroxy-naphthoylamino) 2,4 dimethoxy 5 bromobenzene are used instead of 17.9 parts by weight of l- (2',3.- hydroxy naphthoyl amino) 2,4 dimethoxy 7 S-chlorobenzene, a dyestuff of similar tint is obtained. 0.5 part by-weight of this dyestuif is added to parts by weight of the condensation product of urea and formaldehyde containing 30 per cent of wood dust as a filler and the mixture thus formed is ground for 12 hours in the ball mill. The mass is then placed into a press wherein, during 5 minutes, it is hardened at C. under pressure to the desired moulded body. The dyestulf corresponds to the following formula:

Q ngd- The following table indibates ponents which may be vention and the tints obtained which likewise po's s ess'g gee-gist;

u ibelf hf further. eom

used according to the presentinof the mono-azo-dyestufis thus ood fastness properties.

Diazo Component Coupling Component Tint (1) 1-amino-2-methoxybenzeng-fi-carboxylic acid am e. (2) l-amino-Z-methoxybenzene--carboxylic' acid amide.

(3) 1-amino-2-ethoxybenzene-5-carboxylic aeid.--

mide

(4) 1-amino-2-ethoxybenzeng-fi-carboxylic" acid (5) l-aminofl-ethoxybenzene-5-carboxyl'icacid amide. 1

(6) l-amino-Z-ethoxybeuzene-fi-carboxylie acid amide.

(7) l-amino-2 ethoxybenens-K -earboxylic acid zene-fi-carboxylic acid am e.

(9) 1-amino-2-ethoxybenzene-5-carboxylic acid amide.

1 (2.3' hydroxynaphthoylamino) -2.5 -dimethoxy-4- bromobenzen'e.

2.fi-diethoxyA-chlorobenzene. 2.4-dlmethory-fi-chlorobenzone;

2.5-dimeth'oxy-4-ohlorobenzene.

1-(6-methoxy-2.3'-hydroxynaphthoylamino) 2.4 d1- methoxy-5-ehlorobenzene.

2.4-dimethoxy-o-bromobenzene.

red.

bluishclaret.

bluish-red.

Item 3 c 0NH:

N ll 01 I OH 0011, p

-c 0NH Item 4:

C O-NH| 1 I l 0 OH:

OH or c O-NH 50H, I claim:

1. The mono-azo dyestuffs insoluble in water corresponding to the following general formula I N I wherein one of thet'wo s ubstituentsXi and- X represents a member of the group consisting "of chlorine and bromine, and the other represents v an OR* radical, R stands for one of the group consisting ofmethyl and ethyl, and Y stands for a member of the group consisting of hydrogen, methoxy, and bromine.

2. The mono-azo-dyestuifs insoluble in water corresponding to the following generalformula wherein one of the two substituents X1 and X2 represents a member of the group consisting of chlorine and bromine, and the other represents a methoxy group, and R stands for one of the group consisting of methyl and ethyl.

3. The mono-azo-dyestuif insoluble in water corresponding to the following formula N OCH;

o O--NH born 4 The mono-azo-dyestutf insoluble in water corresponding to the following formula C O-NH:

OHIO- OCH;

OCH:

5. The mono-azo-dyestuff insoluble in water corresponding to the following formula 6. The mono-azo-dyesmfi insolublc in water ponding to the following formula CgHgO- N v 1% OCH: 7

G O-NE'.

- mac- 7. The mono-azo-dyestfifi insoluble, in water ,correspon din g tq the following fcrmula,

' co-Nfi:

' OHIO-- :1 N Br 10 I 01': com

(JO-NE References Cited in'thc file of this ,patnt UNITED STATES PATENTS 1,951,815 Zahn et'al. Mar. 20, 1934 1,964,980 Eichwede July 3, 1934 2,006,211 Fischer June 25, 1935 2,027,897 Bonhote Ian. 14, 1936 

1. THE MONO-AZO DYESTUFFS INSOLUBLE IN WATER CORRESPONDING TO THE FOLLOWING GENERAL FORMULA 